Method of treating oil



Feb. 2, 1937. A. voN GROELING 2,069,596

I vMETHOD OF TREATING OIL Filed Jan. 29, 195o abbr/mmf Patented Feb. 2, 1937 UNITED STATES tasses PATENT OFFICE METHOD 0F TREATING OIL Albrecht von Groeling, Los Angeles, Calif.

Application January 29, 1930, Serial No. 424,254

1 Claim.

This invention relates to a method and means whereby fuel oil may be treated in such a manner as to produce the more valuable hydrocarbon products.

More particularly, the invention has for an object the provision of a method and means which is adapted for cooperation with any type of topping or cracking plant such as for example described in my Patent 1,295,088 and which said invention may utilize the residue oil from said cracking or topping plant to convert said residue oil into higher and more valuable hydrocarbons.

The invention is particularly adaptable to treat residues having free carbon or asphalt which is to be either removed or converted.

Another object is the novel arrangement of various apparatus whereby a cracking of crude oil may be taking place and the residue or uncracked part thereof at the same time utilized in a continuous and circulatory system in such a manner as to be combined with other gases to in turn produce more valuable hydrocarbons.

Another object of this invention is to utilize a series of units in such a manner as to first crack a crude oil and produce a residue, which residue is to in turn be so treated as to turn said residue into valuable hydrocarbon products, to the end that all of said residue is utilized and no waste product or substantially no waste product or residue remains after the several steps in the operation of the apparatus are completed.

Another object is the utilization in certain embodiments of What may be termed a continuous cracking process, the second phase cracker linking the first phase cracker.

Another object of the invention is the provision of a system and means whereby free hydrocarbon can be segregated and in such a manner that the carbon can be converted into light compounds.

`As a brief statement of the invention, it may be said that after the usual fractionation or topping has taken place from the crude oil, to the end that the light weight constituents are ab-I stracted, the residue is treated to produce synthetic gasoline, including heavy naphtha, some kerosene, fuel oil, coke or asphalt. The rst rening process of the said crude will, of course, produce various values such as gasoline, kerosene, andl gas oil. These products the present invention is not particularly interested in. It is in the treating of the residue of the crude after the removal of these products by the first cracking operation that this invention is primarily directed, The second cracking plant is adapted to treat the residue under high temperature and pressure and which temperature and pressure is gradually reduced but not before the residue under high heat and pressure is acted upon by some fluid injected into the same which combines 5 with said residue, whereby the normally uncracked residue which may contain asphalt, and possibly paraffin wax, are converted into light weight hydrocarbons. More especially, the carbon is segregated and converted into hydrocar- 10 bon compounda'which will tend to produce oil out of coke or coal. If natural gases of the parafn' series are used, they are transformed into unsaturates in combining with nascent carbon when set free. 15

Other objectsV of the invention will be set forth as the description of the invention proceeds. v The drawing is` a side elevation, partly diagrammatic and partly in section, of apparatus which may be utilized in carrying out the invention.

Referring to the drawing, I have shown for the purpose of illustration a topping or cracking plant at A, which includes a heater a, a dephlegmator or still b, further dephlegmators c at i and 2, a preheater d, an expander e, and one or more coolers and tanks f as shown at 3, 4, 5, and 6. These series of units may be utilized in cracking a crude oil to derive therefrom various fractions of hydrocarbon such as gasoline, kerosene and the like, and such units in combination represent one form of cracking or topping plant which performs very efficiently the several operations, although Within the scope of the present invention, other types of cracking or topping plants 35 may be as readily utilized.

The crackingor topping plant A is adapted to act in conjunction with means B. The means B is adapted to treat the residue oil from the cracking or topping plant A to produce further valuable hydrocarbon products.` More particularly, the means B includes a heater y, temperature and pressure reducers h, of which there may be a series, as shown at 1, 8 and 9, a dephlegmator 7', and coolers and tanks lc, as shown at ill, Il, l2 and i3. The cooler and tank unit shown at I4 may operate in conjunction with either the cracking'and topping plant A or with the means B for treating the fuel oil. Included in the means B are one or more pumps m and n. 50

The cracking and topping plant A will be first described, followed by a description of the means B for treating the residue or fuel oil after the crude has been cracked by the plant A.

The preheater d includes a tank I5 within 55 1 which is a pipe coil I6 locatedV near the bottom of said tank. A pipe II is received within said tank and has its mouth portion adjacent the bottom --of the tank. A further pipe I8 has theV mouth portion thereof above the pipe coil I6 and leadsV from said tank. The tank is provided with a dome I9.VV A pipe communicates between said dome and the cooler unitY ,f shownat 3, which cooler unit includes the cooler proper and a tank for receiving Vthel condensed huid. T'he pipe I8 is in direct communication with the dephlegmating preheater c, shown at 2. This type o-f dephlegmating preheaterY includes a tank 20 andfa jacket member 2| surrounding the same.V The tank 20 is conventional in form; including the usual baffle plates to cause gases topass therein in a devious path. 'I'he'jacket is closed at both the top and bottom anddoes not entirely sur"- round the tank 2IlV butrmay be spaced above the bottom portion thereof, as shown in the drawing.k

` Y The pipe I8 communicates, as before stated, with K bottom` 240iD the jacket and this pipe 23 in turn f communicates with the preheating dephlegmator Y the spaceY included between the jacket and the perijgilieryY of the tank 20 and adjacent Athe top of .said tank and jacket, asgshownY at 22.Y YA further pipe 23f'has its mouth portion adjacent the vc shownfat Iv in the same manner as for the dev valved' connection 32 with a pump o.

phlegmating preheater shown at 2, both dephlegmating preheaters being identically constructed.

A pipe 25 leads from the jacket of the dephlegmating preheater shown atgI to the `still or dephlegmator b. This pipe terminates with one or more" spray nozzles `V26 positioned adjacent the Ytop of thedephlegmator or still b; This still or pipe 35 with the. heateraz. YThe pump 'o communicates through a valved pipe36 with` a` dehydrationy unit p ofV conventional construction, and a pipeV 31'leads from said unit past a valve 38 to the pipe 33. Likewise said pump ois connected by a pipe-36a to pipe 33. A pipe 39 communicates with theV top ofthe dome 28 and the bottom of the dephlegmator casing orY cylinder 2 0 of the dephlegmating preheater c shown at I, and av pipe V4Ilf communicates with the top of Y the cylinder 20 of the unit shown atl and with the bottom of the cylinder I2() of the unit shown at 2. A pipe 4I is in communication With the top of the cylinder 20of the unit 2 and one of the cooling units f shown at 4. The bottom of the tank 20 of the unit shown at 2 is in communication with the still b through the'medium of a pipeV 42, which includes valves 43 vand 44, thevalve 43 being near the outlet of the tank and the valve 44 adjacentthe still. A further pipe 45 provided with a valve 46 communicates with a further cooling unit f shown at 5. With respect to the dephlegmating preheater shown at I, a pipe 46 is provided with valves 41 and,48 and allows communication between the Vbottom of the tank 20' of this Yparticular unit and with the still b, and a further pipe 49 provided with a valve 5I) communicates with a further cooling unit f shown at 6. Itd will be notedth'at .the valves 43 and 46, 4'8" and 5'0 allow any liquid received Within the .heater c shown at I-. 'flowed into the dephlegmating preheater shown dephlegmating preheater casings 20 a ow path Y in one of two directions or, in certain instances,

in both directions. vThe expander e has a connection through the medium of Va pipe 5I withY the coil I6 inthe preheater d and a valve 52 controls communication between said pipe coil I6 and expander e. Y y

The operation of the cracking or topping plant A is undoubtedly clear to those skilled in the art, but by way of explanation, it may be said that crude oil from. a source'of supply is passed within the preheater tank d through the medium of the pipe II.V This crude oil may pass through the pipe IB into the jackets 2I of the dephlegmatirig preheaters, thence into the still Vb and through thefpipe 33 into the heater aor by closing the"V n valve 53 and opening the valve 32, said fluid maybe pumped by the means o through vthe dehydrating unit p to remove water from the oil, and thence past thevalves-38 and 34, the valve' B5being closed, into the heater at." Orr the residue may be Vforced directly under pressure into the heater a by thev pump o by'closing the valve in pipe 36, closing valve 53, and Yopening opening valve 32. Y In actual practice, the heater a will be filled or partially filled to a desired level therein with crude oil, as would likewise be the` preheater d. The Vpreheater dis 'of the low heat pressure type in the present instance and a tem- Y perature of perhaps 60 to 80 C. is maintained.

However, I do not limit myself to any Yparticular temperature. The heated crude oil from the heater d is directed under pressure reduction past Y the valves 34V and 35 into the expander e. The

lighter vapors of the crude oil are expanded and directed throughthe pipe I8 into the jacket of the dephlegmating preheater c, shown at 2;. VThe hot vapors from the crude oil received within the stillrb in turn are received within the dome 28,'r

and thence conducted by the pipe 39 into the bottom of the tank'20 kof the dephleginating pre- The crude, oil whichhas tween the oil surrounding the tanks 20 and theV vapors therein, with the result that there is a heat exchange therebetween causing a condensation oi' certain of the vapors. In actual practice, the

the still b in the form of a spray through the nozzles 26 and the hot gases within the expander contact with this spray of crude oil and tend to 'crude oil from the preheater d is injected into crack or reexpand certain constituents thereof.

Thus, by closing the valve 48 of the first unit l and opening the valve 50, such residue or condensate may be passed through the pipe 49 and into the cooler units f shown at 6. The residue or condensate in the unit shown at 2 may have the valve 43 closed and the valve 46 opened, in which case said liquid is passed through the pipe 45 into the cooler unit f shown at 5. If separation of these various fractions is not desired, the valves 46 and 50 may be closed and the valves 43 and 48 opened, in which instance the residues or condensates are conducted by pipes 42 and 46 into the dephlegmator or still by where they are acted upon by the hot gases from the expander e whereby further extraction of essential hydrocarbon results. As a consequence, a continuing cracking of the oil takes place. Or, if desired, a certain portion of this crude, which does not vaporize, may be passed through the pipe 3| and again forced into the heater d through the medium of the pump 0, together with the fresh oil coming from above. Of course, the pump has always to operate, to the end that a desired pressure may be maintained within the heater a while the dehydrator may be eliminated if no water is to be abstracted. It will thus be seen that the oil which is passed from the heater ai, and which has been expanded in the expander e thence passed into the still b and from there into the dephlegmating preheaters, is progressively cooled and condensed while the incoming oil from the preheater d which is caused to flow within the dephlegmating preheater jackets and which flows in an opposite direction from the movement ofthe oil from the. heater a., is progressively heated; this incoming oil from the preheater d acting as a condenser for the vaporized crude from the heater a and this Vapor and condensate from the heater ca acting to preheat the incoming crude oil from the preheater d. Consequently, there is a continuous heat exchange.

It will be noted that a pipe allows communication between the cooler f shown at 3 and the dome i9 above the preheater column or casing l5. Thus, the apparatus is so arranged that a rough separation of Values from the crude oil within the preheater d may be effected by the application of heat at one point only, namely, in the heater a, which heat is utilized for preheating the incoming crude oil within the preheater d by passing the residue of the crude oil within the expander through the pipe coil I6. The number of dephlegmating preheaters may be varied at will as may likewise the number of coolers f.

The means B is utilized for further obtaining valuable hydrocarbon constituents from the residue of the crude oil which have not been dephlegmated, or which have not been extracted by the various dephlegmating preheaters and stored within certain of the cooler tanks ,'f from the cracking or topping plant A. For instance, the condensate or residue oil from the expander e may be directly passed by means of the pump n into the heater g', or the hot oil which has been circulated through the pipe I6 may be directed to said heater g through the medium of a pipe 54. This pipe is not continuo-us but broken in that said pipe has included therein valves at 55, 56, 5l, 58 and 59. Furthermore, the said pipe includes a cross-head coupling 66, as well as couplings 6|, 62, 63, 64, 65 and 66. The pipe 6l from the coil leads to the valve 55 and likewise leads to a valve 63 communicating with a cooler shown at I4. From the coupling 66, the pipe 54 has a connection with the pump n and from said pump continues to the heater g. This latter pipe, before entering the heater g, has interposed therein a valve 69. Temperature and pressure reducers h are shown at 1, 8 and 9. These temperature and pressure reducers are conventional in form, the `rst one shown at 1 being in section, wherein it will be seen that the same includes a casing 'I6 in communication with a plurality of tubes ll, the tubes in turn communicating with dome 12. 'I3 and the construction is such that fluid may be passed around the tubes without in any manner being received within the dome l2 or within the casing 79 and in the manner illustrated. Valved pipes 74 and I5 communicate with upper and lower portions of the casing 'i3 surrounding the tubes and said pipes are connected to the couplings 64 and 65. It will be observed that the valve 58 is interposed between couplings 54 and 65. The next two temperature and vpressure reducers h shown at 8 and 9 are similarly constructed and Valved pipes 16 and 11 communicate with the casing I3 thereof and with the couplings 62 and 63 for the unit shown at S, while Valved pipes 58 and 19 communicate with the casing 'I3 and couplings 60 and 6| for the unit shown at 9. A pipe 36, provided adjacent its ends with valves 8E and 82, communicates between the heater g and the casing 'i9 of the unit at T. A pipe 83 communicates with the dame 12 and through a valve 94 with the bottom of the casing l0 of the unit at 8. A pipe 85 communicates with the dome 12 for the unit at 8 and through a valve 86 with the casing 16 for the unit at 9. pipe 81 communicates with the dome l2 of the unit at 9 and thence through a valve 88 with the dephlegmator i. This dephlegmator may have Surrounding these tubes is a casing` therein the usual baffle plates., whereby various vapors may be segregated and passed through pipes arranged at different levels of said dephlegmator for further passage into the coolers k. shown at l0 and ll. Of course, the number of dephlegmators and coolers may be varied in accordance with use and practice. Residue from the dephlegmator may be collected and passed through Valved pipes 89 and 90. Valved pipe 99 leads to the cooler unit 7c shown at I3 while the Valved pipe 89 is associated with the cross-head coupling 69. The pump m is in communication with the heater o through a valve-d pipe 9| and another pipe 99 communicates with the pump and with some source of Huid supply, which fluid is to be forced within the heater g by the said pump m. The character of the fluid which is forced by the pump m into the heater may be varied. For instance, petroleum distillate, natural gas, hydrogen, or other gases may be utilized.

The purpose of the temperature and pressure reducers is to gradually reduce in consecutive steps, temperature and pressure of the vapor or fluid passed therein.

While I do not wish to be restricted in this invention to any particular temperature or pressure, it may be said that the fluid received within the heater g may be maintained at 1000, more or less, F., and possibly pressures of 50 to 70. or less or more, atmospheres maintained therein. The petroleum distillates, natural gas, hydrogen, or other gases, are forced by the pumpm into this heater and the high heat plus the high pressure is suflicient to cause these gases, distillates or the like, to combine with the fluid passed within said heater, either directly from the coil I6, or the residue from the expander e. Forcing the natural gas, hydrogen, or the like into the residue oil from the rst cracking or topping plant lowers the specific gravity of the oil and causes a further cracking op-eration. However,

Ain order to make the gas, latently formed Aby. this Vand this expansion Valve works in the ordinary Vmannen-namely, to open when the pressure is reduced below a certain amount in the means h whereby further fluid may be admitted therein, and to close when the pressure therein exceeds a certain amount.'V VThis gaseousiuid'will pass upwardly through the p-ipe 1I` and outwardly through the dome 'IZVintc the pipe 831where it is passed into the temperature and pressure reducer shown at 8. There is included within the'line 83 a pressure reduction valve 815, similar tothe valve 182. Again the sequence of operation-takes place, and the gases pass through the pipe into the temperature and pressure reducer h shown at 9, the admittance of which is controlled by the reduction valve 86.- Thence, the gaseous fluidis passed through the pipe 81 past the Valve 88 into the dephlegmator 7'. During all this time, the fluid which has passed through thepipe I and which initially warms the crude oil within the preheater d is passed into the jacket T3 surrounding the pipes ll. As this fluid is initially cooler than the gaseous fluid flowing through the pipe TI, a heate'xchangewill occur. -It'will be noted that this-'fluid may be forced through the jackets of` each of the temperature and pressure reducers by proper control'of .the valves 55, 5'! a-nd- .58r in one i-nstance to close the same, and open-ing the valves'inthe pipes 14 to 19 inclusive. Of course, the number of temperature and pressure reducers may be varied at will, as may likewise bevaried the' number of dephlegmators y'. It will be noted that pipes are in communication with different levels-.ofthe dephlegmator :i and the cooler' units-1e shown` at l0 and Il, whereby different fractions'ofgases which have been condensed may be received within the tanks thereof. A 'gradual reduction of'ternperature and pressure is Yof course' necessaryin order toV obtain .the vaporsfandVV condensatesfdesired and for Ygood practice. TheV` initial forcing under pressure of the natural gas'jhydrogen or other gases, into the. residue Vwithin the' heater, which has beenV passed therein from the expander, tends to lower Y the specific gravity of the oil therein, vand quite obviously the processes which thereafter follow and the number thereof Will depend upon the gravity of oil nally desired. It is, kof course,

1 realized that if it is not desired to use the oil fromthe coil l5, as the circulating mediur'mother fluids could beY used, Ordinarily, the heavy residues received within. the. heater o' containV asphalt and carbon` in large quantities and by the method which has just been described, itis possible to effect the conversion of the asphalt and free carbon into lightfractions. The converted liquid is cooled down and the pressure reduced to the extent that finally by the vlast reduction, the expanded product is at barometric pressure and the` latently converted fractions developed into gasiform which can be rectified by the dephlegmators i, then separated and conden'sedV in the coolers and tank devices k. The residue may be received in the tankv k shown-at I3 or passed into the pipe line 54 or IningledY with theroil passed through the coilY I6 as will be observed'is possible-due to the method of interconnectingV the different pipes (see crosshead union (ill).` The cooling down and reduction of pressure kfrom temperature'and pressure reducer vto temperature and pressure Vreducer must always'be governed bythe principle that thetemperature within any cooler must be Yin` relative relation to the end that the heaviest product o-f fluid therein shall have no tendency to vaporize in such cooler'and the tendency to Y vaporize shall only commence at the last temperature and Vpressure reducer, Vat which'time the reduction tends to the barometric pressure,V

When the barometricV pressure finally obtains, then alll the fractionsv within Vthe latently converted liquidV will have -vaporized It is evident that the liquid flowing through the pipe 54 into the first temperature and pressure reducer shown at 8 will be cooler than it will be subsequently s and therefore the arrangement shown works ad- Y vantageously to effect the result Vfinally sought.

In the preceding description, a system of.v dis-V tillation is shown which'answers toY all `the needs of a modern refinery. Even vacuum distillations can be attached, in connecting the system A with a high vacuum plant. In that case, the light be abstracted just as above described but then the residues should be delivered Yto thehigh vacuum plant., This has the great advantage that it allows the hotresidues before they are injected openly into the vacuum and distilling plant, to

do the heating while passing through 'the coils The method whereby fuel oil may be treated i to produce more vvaluable Yhydrocarbon products,

which consists in first fractionating a crude oilV to remove the light weight constituents therefrom and leave a residue, treating the residue under a temperature of approximately 1000` F., j

more or less, and a pressure of 50 to 70 atmospheres,and atthe same' time injecting into said residue a fluid selected from theV group comprising hydrogen and natural gas and adapted to combine with said residue, to form lower boiling hydrocarbons, and thereafter passing the products of the thus treated residue through a seriesy of temperature and pressure reducing stages, correlating the temperature and pressure in each stage so that the heavier portions of treated residue products do not vaporize therein, and in the last stage vaporizing the lower boiling hydrocarbon product of the -treated residue.

-' ALBRECHT voN GROELING.

35 fractions, as gasoline and heavy napht'ha,` may Y Y 

